CN102809897B - Hardening resin composition - Google Patents
Hardening resin composition Download PDFInfo
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- CN102809897B CN102809897B CN201210170207.4A CN201210170207A CN102809897B CN 102809897 B CN102809897 B CN 102809897B CN 201210170207 A CN201210170207 A CN 201210170207A CN 102809897 B CN102809897 B CN 102809897B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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Abstract
Offer can form the film of excellent heat resistance and the hardening resin composition of pattern.【Solution】Hardening resin composition, it contains：（A）Containing come from least one construction unit in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and come from the unsaturated compound with Oxyranyle the addition polymers of construction unit,（B）Have the compound of at least one group in acryloyl group and methylacryloyl,（C）Polymerization initiator and（D）Formula（1）Shown compound, formula（1）In, R1Expression benzyl or the cyanoalkyl that carbon number is 2～5, R2～R4Represent the acyl group that alkyl, phenyl, nitro or the carbon number that hydrogen atom, halogen atom, carbon number are 1～20 is 1～20 independently of each other, the hydrogen atom containing in this alkyl and this phenyl can be optionally substituted by a hydroxyl group.
Description
Technical field
The present invention relates to hardening resin composition.
Background technology
In liquid crystal indicator etc., the film of color filter protecting layer etc. can use as component.Color filter protecting layer, be
For making as the color filter of ground or the concavo-convex planarization on produced surface in black matrix or being used for protecting color filter etc. and make
It is from from for forming the film of the infringement of the medicinal liquid of the component on its upper strata.In order to form color filter protecting layer, can make
Use hardening resin composition.
As this hardening resin composition it is known that for example containing unsaturated carboxylic acid and aliphatic polycycle epoxy compound
The hardening resin composition of the copolymer of thing, dipentaerythritol acrylate and polymerization initiator（Patent documentation 1）.
【Patent documentation 1】Japanese Unexamined Patent Publication 2010-152335 publication.
Content of the invention
For the film being formed using the above-mentioned hardening resin composition being currently known or pattern, its thermostability may not be sufficient
Enough height, have the situation being easy to coloring by heat treated.
The invention provides following ［ 1 ］～［ 4 ］.
［ 1 ］ hardening resin composition, it contains following（A）、（B）、（C）With（D）,
（A）Contain and come from least one construction unit in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and come from
There are the addition polymers of the construction unit of the unsaturated compound of Oxyranyle
（B）There is the compound of at least one group in acryloyl group and methylacryloyl
（C）Polymerization initiator
（D）Formula（1）Shown compound
【Change 1】
［ formula（1）In, R1Expression benzyl or the cyanoalkyl that carbon number is 2～5,
R2～R4Represent independently of each other alkyl, phenyl, nitro that hydrogen atom, halogen atom, carbon number are 1～20 or
Carbon number is 1～20 acyl group, and the hydrogen atom containing in this alkyl and this phenyl can be optionally substituted by a hydroxyl group ］.
［ 2 ］ hardening resin composition as described in above-mentioned ［ 1 ］, wherein,（D）Content with respect to（A）100 mass parts are
1 mass parts～25 mass parts.
［ 3 ］ film, it utilizes the hardening resin composition described in above-mentioned ［ 1 ］ or ［ 2 ］ to be formed.
［ 4 ］ display device, it contains the film as described in above-mentioned ［ 3 ］.
According to the hardening resin composition of the present invention, can be formed the coloring being led to by heat treated less, thermostability excellent
Different film or pattern.
Specific embodiment
Hereinafter, the present invention is described in detail.
The hardening resin composition of the present invention contains addition polymers（Hereinafter sometimes referred to " polymer（A）”）, this addition polymers
Contain and come from least one construction unit in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and come from oxirane
The construction unit of the unsaturated compound of base.
As polymer（A）, can enumerate for example
Polymer ［ A1 ］：By at least one in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides（a）（Hereinafter sometimes referred to
“（a）”）, and there is the unsaturated compound of Oxyranyle（b）（Hereinafter sometimes referred to "（b）”）The copolymerization being polymerized
Thing,
Polymer ［ A2 ］：Will（a）With（b）, and can be with（a）With（b）The monomer of copolymerization（c）（Wherein, be with（a）With（b）No
Same monomer）（Hereinafter sometimes referred to "（c）”）Copolymer being polymerized etc..
（a）Acrylic acid, methacrylic acid .beta.-methylacrylic acid, adjacent vinyl benzoic acid, a vinyl benzene specifically can be enumerated
Formic acid, the unsaturated monocarboxylic class to vinyl benzoic acid etc.；
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acid, 4- vinyl neighbour's benzene
Dioctyl phthalate, 3,4,5,6- tetrahydrophthalic acid, 1,2,3,6- tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid,
The unsaturated dicarboxylic class of Isosorbide-5-Nitrae-cyclohexene dioctyl phthalate etc.；
Methyl -5- norborene -2,3- dioctyl phthalate, 5- carboxyl bicyclic ［ 2.2.1 ］ hept-2-ene", 5,6- dicarboxyl
Base bicyclic ［ 2.2.1 ］ hept-2-ene", 5- carboxyl -5- methyl bicycle ［ 2.2.1 ］ hept-2-ene", 5- carboxyl -5- ethyl
Bicyclic ［ 2.2.1 ］ hept-2-ene", 5- carboxyl -6- methyl bicycle ［ 2.2.1 ］ hept-2-ene", 5- carboxyl -6- ethyl are double
The bicyclic unsaturated compound class containing carboxyl such as ring ［ 2.2.1 ］ hept-2-ene"；
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acid acid anhydride, 4- vinylphthalic acid
Acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic acid
Acid anhydride, bicyclic ［ 2.2.1 ］ hept-2-ene" -5, the unsaturated dicarboxylic anhydride of 6- dicarboxylic anhydride etc.；
Mono succinate (2-（Methyl）Acryloyl-oxyethyl) ester, phthalic acid list (2-（Methyl）Acryloxy
Ethyl) more than 2 yuan of the polybasic carboxylic acid such as ester unsaturated single (（Methyl）Acryloxyalkyl) esters；
α-（Hydroxymethyl）Acrylic acid is such, the unsaturated acrylate containing hydroxyl and carboxyl in same molecule
Class etc..
Wherein, from the point of view of copolyreaction, alkali-solubility, acrylic acid, methacrylic acid, maleic acid are preferably used
Acid anhydride etc..
In this specification, "（Methyl）Acrylic acid " represents at least one in acrylic acid and methacrylic acid.“（First
Base）Acryloyl group " and "（Methyl）The statement of acrylate " etc. also has the same meaning.
In the present invention, there is the unsaturated compound of Oxyranyle（b）Refer to oxirane ring and unsaturated bond
Monomer.（b）Can enumerate and for example there is structure and the ethylene unsaturated bond that chain type unsaturated aliphatic hydrocarbon has been at least partially epoxidized
Monomer（b1）（Hereinafter sometimes referred to "（b1）”）, or there is the structure that ester ring type unsaturated hydrocarbons have been at least partially epoxidized and ethylene not
The monomer of saturated bond（b2）（Hereinafter sometimes referred to "（b2）”）.
In the present invention,（b）Preferably there is Oxyranyle and the monomer of ethylene unsaturated bond, more preferably there is ring
Oxirane group and（Methyl）The monomer of acryloxy.In addition,（b）Preferably（b2）.
As（b1）, specifically, can enumerate（Methyl）Glycidyl acrylate,（Methyl）Propenoic acid beta-first
Base glycidyl esters,（Methyl）Propenoic acid beta-ethyl glycidyl base ester, glycidyl vinyl ether, adjacent vinyl benzyl
Base glycidyl ether, a vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl-neighbour
A vinylbenzyl glycidyl base ether, Alpha-Methyl-vinylbenzyl glycidyl base ether, Alpha-Methyl-to vinyl benzyl
Base glycidyl ether, 2,3- are double（Glycidyl oxy methyl）Styrene, 2,4- are double（Glycidyl oxy methyl）
Styrene, 2,5- are double（Glycidyl oxy methyl）Styrene, 2,6- are double（Glycidyl oxy methyl）Styrene, 2,
3,4- tri-（Glycidyl oxy methyl）Styrene, 2,3,5- tri-（Glycidyl oxy methyl）Styrene, 2,3,6-
Three（Glycidyl oxy methyl）Styrene, 3,4,5- tri-（Glycidyl oxy methyl）Styrene, 2,4,6- tri-（Contracting
Water glyceryl epoxide methyl）Compound described in styrene, Japanese Unexamined Patent Publication 7-248625 publication etc..
As（b2）, a vinylcyclohexene oxide, 1,2- epoxy -4- vinyl cyclohexane can be enumerated（Such as セ
ロキサイド2000；ダ イ セ Le chemical industry（Strain）System）, acrylic acid 3,4- epoxycyclohexyl-methyl ester（Such as サ イ Network
ロマーA400；ダ イ セ Le chemical industry（Strain）System）, methacrylic acid 3,4- epoxycyclohexanecarboxylate（Such as サ イ Network ロ
マーM100；ダ イ セ Le chemical industry（Strain）System）, formula（I）Shown compound, formula（II）Shown compound etc..
【Change 2】
In formula（I）And formula（II）In, R1And R2Represent hydrogen atom or alkyl that carbon number is 1～4 independently of each other, should
The hydrogen atom containing in alkyl can be optionally substituted by a hydroxyl group.
X1And X2Represent singly-bound ,-R independently of each other3-, *-R3- O-, *-R3- S-, *-R3- NH-.
R3Represent the alkane diyl that carbon number is 1～6.
* represent the associative key with O（Close handss）.
The alkyl being 1～4 as carbon number, specifically, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, positive fourth
Base, sec-butyl, tert-butyl group etc..
Hydroxy alkyl can enumerate hydroxymethyl, 1- hydroxyethyl, 2- hydroxyethyl, 1- hydroxypropyl, 2- hydroxyl
Propyl group, 3- hydroxypropyl, 1- hydroxyl -1- Methylethyl, 2- hydroxyl -1- Methylethyl, 1- hydroxybutyl, 2- hydroxyl
Base butyl, 3- hydroxybutyl, 4- hydroxybutyl etc..
R1And R2Hydrogen atom, methyl, hydroxymethyl, 1- hydroxyethyl, 2- hydroxyethyl can preferably be enumerated, more preferably
Enumerate hydrogen atom, methyl.
Alkane diyl can enumerate methylene, ethylidene, propane -1,2- diyl, propane -1, and 3- diyl, butane -
Isosorbide-5-Nitrae-diyl, pentane -1,5- diyl, hexane -1,6- diyl etc..
X1And X2Singly-bound, methylene, ethylidene, *-CH can preferably be enumerated2- O-（* represent the associative key with O）
Base, *-CH2CH2- O- base, more preferably enumerates singly-bound, *-CH2CH2- O- base.
As formula（I）Shown compound, can be with enumerative（I-1）～formula（I-15）Shown compound etc..Preferably
Enumerative（I-1）, formula（I-3）, formula（I-5）, formula（I-7）, formula（I-9）, formula（I-11）～formula（I-15）.More preferably
Enumerative（I-1）, formula（I-7）, formula（I-9）, formula（I-15）.
【Change 3】
【Change 4】
As formula（II）Shown compound, can be with enumerative（II-1）～formula（II-15）Shown compound etc..Excellent
Select enumerative（II-1）, formula（II-3）, formula（II-5）, formula（II-7）, formula（II-9）, formula（II-11）～formula（II-
15）.
More preferably enumerative（II-1）, formula（II-7）, formula（II-9）, formula（II-15）.
【Change 5】
【Change 6】
Formula（I）Shown compound and formula（II）Shown compound can individually using it is also possible to by two or more
It is used in combination.When by formula（I）Shown compound and formula（II）Shown compound used time, its ratio (formula（I）：Formula（II）〕（Rub
You compare）It is arbitrary, but preferably 5：95～95：5, more preferably 10：90～90：10, particularly preferred 20：80～80：20.
（c）Can enumerate for example（Methyl）Acrylic acid methyl ester.,（Methyl）Ethyl acrylate,（Methyl）N-butyl acrylate,
（Methyl）Sec-butyl acrylate,（Methyl）Acrylate tert-buthyl etc.（Methyl）Alkyl-acrylates；
（Methyl）Cyclohexyl acrylate,（Methyl）Acrylic acid 2- methyl cyclohexane base ester, three ring ［ 5.2.1.02,6The last of the ten Heavenly stems
Alkane -8- base（Methyl）Acrylate（In the art, as trivial name, referred to as（Methyl）Acrylic acid bicyclopentyl ester）、
（Methyl）Acrylic acid bicyclopentyl epoxide ethyl ester,（Methyl）Isobornyl acrylate etc.（Methyl）Acrylate base ester
Class；
（Methyl）Phenyl acrylate,（Methyl）Benzyl acrylate etc.（Methyl）Acrylic acid aryl or aralkyl ester
Class；
The dicarboxylic diester of ethyl maleate., DEF, diethyl itaconate etc.；
（Methyl）2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid 2- hydroxy-propyl ester etc.（Methyl）Acrylic acid hydroxyl
Base alkyl esters；
Bicyclic ［ 2.2.1 ］ hept-2-ene", 5- methyl bicycle ［ 2.2.1 ］ hept-2-ene", 5- ethyl bicyclic ［ 2.2.1 ］
Hept-2-ene", 5- hydroxyl bicyclic ［ 2.2.1 ］ hept-2-ene", 5- hydroxymethyl bicyclic ［ 2.2.1 ］ hept-2-ene", 5-
（2 '-hydroxyethyl）Bicyclic ［ 2.2.1 ］ hept-2-ene", 5- methoxyl group bicyclic ［ 2.2.1 ］ hept-2-ene", 5- ethyoxyl are double
Ring ［ 2.2.1 ］ hept-2-ene", 5,6- dihydroxy bicyclic ［ 2.2.1 ］ hept-2-ene", 5,6- bis-（Hydroxymethyl）Bicyclic
2.2.1 ］ hept-2-ene", 5,6- bis-（2 '-hydroxyethyl）Bicyclic ［ 2.2.1 ］ hept-2-ene", 5,6- dimethoxy bicyclic
2.2.1 ］ hept-2-ene", 5,6- diethoxy bicyclic ［ 2.2.1 ］ hept-2-ene", 5- hydroxy-5-methyl base bicyclic ［ 2.2.1 ］
Hept-2-ene", 5- hydroxyl -5- ethyl bicyclic ［ 2.2.1 ］ hept-2-ene", 5- methylol -5- methyl bicycle ［ 2.2.1 ］
Hept-2-ene", 5- tert-butoxycarbonyl bicyclic ［ 2.2.1 ］ hept-2-ene", 5- cyclohexyl Epoxide carbonyl bicyclic ［ 2.2.1 ］
Hept-2-ene", 5- phenyloxycarbonyl bicyclic ［ 2.2.1 ］ hept-2-ene", 5,6- are double（Tert-butoxycarbonyl）Bicyclic ［ 2.2.1 ］
Hept-2-ene", 5,6- are double（Cyclohexyl Epoxide carbonyl）The bicyclic unsaturated compound class of bicyclic ［ 2.2.1 ］ hept-2-ene" etc.；
N-phenylmaleimide, N- N-cyclohexylmaleimide, N- benzyl maleimide, N- butanimide
Base -3- maleimidobenzoyl ester, N- succinimido -4- malimidobutanoate, N- butanimide
Base -6- maleimidohexanoic acid ester, N- succinimido -3- maleimidopropionic acid ester, N-（9- acridinyl）Horse
Carry out the dicarbonyl imides derivatives class of acid imide etc.；
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene
The phenylethylene of ethylene etc.；
The vinyl cyanide of acrylonitrile, methacrylonitrile etc.；The ethylene of vinyl chloride, vinylidene chloride, vinyl-acetic ester etc.
Based compound class；The acrylic amide of acrylamide, Methacrylamide etc.；1,3-butadiene, isoprene, 2,3- diformazan
The diolefin compound class of base -1,3-butadiene etc.；
3- methyl -3- methacryloxymethyl oxetanes, 3- methyl -3- acryloyloxymethyl oxygen
Azetidine, 3- ethyl -3- methacryloxymethyl oxetanes, 3- ethyl -3- acryloyloxymethyl
Oxetanes, 3- methyl -3- methacryloxyethyl oxetanes, 3- methyl -3- acryloxy second
Base oxetanes, 3- ethyl -3- methacryloxyethyl oxetanes, 3- ethyl -3- acryloxy
Ethyloxetane etc. is containing oxetanyl（Methyl）Esters of acrylic acid；
Acrylic acid tetrahydro furfuryl ester（For example double U ト V#150, Osaka Organic Chemical Industry（Strain）System）, methacrylic acid
Tetrahydro furfuryl ester etc. is containing tetrahydrofuran base（Methyl）Esters of acrylic acid etc..
Wherein, from the point of view of copolyreaction and alkali-solubility, preferably styrene, N-phenylmaleimide,
N- N-cyclohexylmaleimide, N- benzyl maleimide, bicyclic ［ 2.2.1 ］ hept-2-ene" etc..
In polymer ［ A1 ］, the ratio of construction unit coming from each monomer is with respect to the construction unit constituting polymer ［ A1 ］
Total molal quantity, preferably following scope.
Come from（a）Construction unit；5～60 moles of %（More preferably 10～50 moles %）
Come from（b）Construction unit；40～95 moles of %（More preferably 50～90 moles %）
If the ratio of the construction unit of polymer ［ A1 ］ is in above-mentioned scope, there is storage stability, gained film
Chemical proofing, thermostability and mechanical strength trend.
Polymer ［ A1 ］ may be referred to such as document " Polymer Synthesizing method "（The grand row in big Tianjin writes sale room（Strain）
Chemistry was issued with people's the 1st edition the 1st brush on March 1st, 1972）Described in method and the citation described in the document entering
Row manufactures.
Specifically, following methods have been enumerated, i.e. by ormal weight（a）With（b）, polymerization initiator and solvent etc. load
To in reaction vessel, replace oxygen, the method be thus stirred in deoxidizing atmosphere, heat, being incubated using nitrogen.And, wherein
Polymerization initiator used and solvent etc. are not particularly limited, it is possible to use any material usually used in this field.For example,
Polymerization initiator can enumerate azo-compound（2,2 '-azobis isobutyronitrile, 2,2 '-azo is double（2,4- methyl pentane nitriles）
Deng）Or organic peroxide（Benzoyl peroxide etc.）, as long as solvent can dissolve the solvent of each monomer, it is possible to use under
Solvent stated etc. is as the solvent of the hardening resin composition of the present invention（E）.
And, the copolymer of gained directly using reacted solution, or using concentrating or can dilute
Solution, or method by the use of reprecipitation etc. can also be used as solid（Powder body）The material taking out.Especially, in this polymerization
When, by using with following solvents（E）It is used as solvent for identical solvent, can directly reacted solution be used for solid
The manufacturing process of hardening resin composition can be simplified by the preparation of the property changed resin combination.
In polymer ［ A2 ］, with respect to the total molal quantity of the entire infrastructure unit constituting polymer ［ A2 ］, come from each
The ratio of the construction unit of monomer is preferably following scope.
Come from（a）Construction unit；2～40 moles of %（More preferably 5～35 moles %）
Come from（b）Construction unit；2～95 moles of %（More preferably 5～80 moles %）
Come from（c）Construction unit；1～65 mole of %（More preferably 1～60 mole %）
In addition, coming from（a）Construction unit with come from（b）Construction unit total with respect to constituting polymer ［ A2 ］
The total molal quantity of entire infrastructure unit, preferably 70～99 moles %, more preferably 90～99 moles %.
If the ratio of the construction unit of polymer ［ A2 ］, in above-mentioned scope, has the film of storage stability, gained
Chemical proofing, thermostability and mechanical strength tendency.
Polymer ［ A2 ］ can be manufactured using the method same with polymer ［ A1 ］.
As the specific example of polymer ［ A1 ］, can enumerate（Methyl）Acrylic acid/formula（I-1）Copolymer,（Methyl）
Acrylic acid/formula（I-2）Copolymer,（Methyl）Acrylic acid/formula（I-3）Copolymer,（Methyl）Acrylic acid/formula（I-4）'s
Copolymer,（Methyl）Acrylic acid/formula（I-5）Copolymer,（Methyl）Acrylic acid/formula（I-6）Copolymer,（Methyl）Propylene
Acid/formula（I-7）Copolymer,（Methyl）Acrylic acid/formula（I-8）Copolymer,（Methyl）Acrylic acid/formula（I-9）Copolymerization
Thing,（Methyl）Acrylic acid/formula（I-10）Copolymer,（Methyl）Acrylic acid/formula（I-11）Copolymer,（Methyl）Propylene
Acid/formula（I-12）Copolymer,（Methyl）Acrylic acid/formula（I-13）Copolymer,（Methyl）Acrylic acid/formula（I-14）'s
Copolymer,（Methyl）Acrylic acid/formula（I-15）Copolymer,（Methyl）Acrylic acid/formula（II-1）Copolymer,（Methyl）Third
Olefin(e) acid/formula（II-2）Copolymer,（Methyl）Acrylic acid/formula（II-3）Copolymer,（Methyl）Acrylic acid/formula（II-4）
Copolymer,（Methyl）Acrylic acid/formula（II-5）Copolymer,（Methyl）Acrylic acid/formula（II-6）Copolymer,（Methyl）
Acrylic acid/formula（II-7）Copolymer,（Methyl）Acrylic acid/formula（II-8）Copolymer,（Methyl）Acrylic acid/formula（II-
9）Copolymer,（Methyl）Acrylic acid/formula（II-10）Copolymer,（Methyl）Acrylic acid/formula（II-11）Copolymer,
（Methyl）Acrylic acid/formula（II-12）Copolymer,（Methyl）Acrylic acid/formula（II-13）Copolymer,（Methyl）Acrylic acid/
Formula（II-14）Copolymer,（Methyl）Acrylic acid/formula（II-15）Copolymer,（Methyl）Acrylic acid/formula（I-1）/ formula
（II-1）Copolymer,（Methyl）Acrylic acid/formula（I-2）/ formula（II-2）Copolymer,（Methyl）Acrylic acid/formula（I-
3）/ formula（II-3）Copolymer,（Methyl）Acrylic acid/formula（I-4）/ formula（II-4）Copolymer,（Methyl）Acrylic acid/formula
（I-5）/ formula（II-5）Copolymer,（Methyl）Acrylic acid/formula（I-6）/ formula（II-6）Copolymer,（Methyl）Propylene
Acid/formula（I-7）/ formula（II-7）Copolymer,（Methyl）Acrylic acid/formula（I-8）/ formula（II-8）Copolymer,（Methyl）
Acrylic acid/formula（I-9）/ formula（II-9）Copolymer,（Methyl）Acrylic acid/formula（I-10）/ formula（II-10）Copolymer,
（Methyl）Acrylic acid/formula（I-11）/ formula（II-11）Copolymer,（Methyl）Acrylic acid/formula（I-12）/ formula（II-12）'s
Copolymer,（Methyl）Acrylic acid/formula（I-13）/ formula（II-13）Copolymer,（Methyl）Acrylic acid/formula（I-14）/ formula
（II-14）Copolymer,（Methyl）Acrylic acid/formula（I-15）/ formula（II-15）Copolymer,（Methyl）Acrylic acid/formula
（I-1）/ formula（I-7）Copolymer,（Methyl）Acrylic acid/formula（I-1）/ formula（II-7）Copolymer .beta.-methylacrylic acid/formula（I-
1）Copolymer .beta.-methylacrylic acid/formula（I-2）Copolymer .beta.-methylacrylic acid/formula（I-3）Copolymer .beta.-methylacrylic acid/formula（I-4）'s
Copolymer .beta.-methylacrylic acid/formula（I-5）Copolymer .beta.-methylacrylic acid/formula（I-6）Copolymer .beta.-methylacrylic acid/formula（I-7）Copolymerization
Thing .beta.-methylacrylic acid/formula（I-8）Copolymer .beta.-methylacrylic acid/formula（I-9）Copolymer .beta.-methylacrylic acid/formula（I-10）Copolymer,
.beta.-methylacrylic acid/formula（I-11）Copolymer .beta.-methylacrylic acid/formula（I-12）Copolymer .beta.-methylacrylic acid/formula（I-13）Copolymer, bar
Bean acid/formula（I-14）Copolymer .beta.-methylacrylic acid/formula（I-15）Copolymer .beta.-methylacrylic acid/formula（II-1）Copolymer, Fructus Crotonis
Acid/formula（II-2）Copolymer .beta.-methylacrylic acid/formula（II-3）Copolymer .beta.-methylacrylic acid/formula（II-4）Copolymer, Fructus Crotonis
Acid/formula（II-5）Copolymer .beta.-methylacrylic acid/formula（II-6）Copolymer .beta.-methylacrylic acid/formula（II-7）Copolymer, Fructus Crotonis
Acid/formula（II-8）Copolymer .beta.-methylacrylic acid/formula（II-9）Copolymer .beta.-methylacrylic acid/formula（II-10）Copolymer, Fructus Crotonis
Acid/formula（II-11）Copolymer .beta.-methylacrylic acid/formula（II-12）Copolymer .beta.-methylacrylic acid/formula（II-13）Copolymer, bar
Bean acid/formula（II-14）Copolymer .beta.-methylacrylic acid/formula（II-15）Copolymer, maleic acid/formula（I-1）Copolymer, horse
Carry out sour/formula（I-2）Copolymer, maleic acid/formula（I-3）Copolymer, maleic acid/formula（I-4）Copolymer, maleic acid/
Formula（I-5）Copolymer, maleic acid/formula（I-6）Copolymer, maleic acid/formula（I-7）Copolymer, maleic acid/formula
（I-8）Copolymer, maleic acid/formula（I-9）Copolymer, maleic acid/formula（I-10）Copolymer, maleic acid/formula（I-
11）Copolymer, maleic acid/formula（I-12）Copolymer, maleic acid/formula（I-13）Copolymer, maleic acid/formula（I-
14）Copolymer, maleic acid/formula（I-15）Copolymer, maleic acid/formula（II-1）Copolymer, maleic acid/formula（II-
2）Copolymer, maleic acid/formula（II-3）Copolymer, maleic acid/formula（II-4）Copolymer, maleic acid/formula（II-5）
Copolymer, maleic acid/formula（II-6）Copolymer, maleic acid/formula（II-7）Copolymer, maleic acid/formula（II-8）'s
Copolymer, maleic acid/formula（II-9）Copolymer, maleic acid/formula（II-10）Copolymer, maleic acid/formula（II-11）'s
Copolymer, maleic acid/formula（II-12）Copolymer, maleic acid/formula（II-13）Copolymer, maleic acid/formula（II-14）
Copolymer, maleic acid/formula（II-15）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-1）Copolymer,（First
Base）Acrylic acid/maleic anhydride/formula（I-2）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-3）Copolymer,
（Methyl）Acrylic acid/maleic anhydride/formula（I-4）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-5）Copolymerization
Thing,（Methyl）Acrylic acid/maleic anhydride/formula（I-6）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-7）Be total to
Polymers,（Methyl）Acrylic acid/maleic anhydride/formula（I-8）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-9）'s
Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-10）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-
11）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-12）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula
（I-13）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-14）Copolymer,（Methyl）Acrylic acid/maleic acid
Acid anhydride/formula（I-15）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-1）Copolymer,（Methyl）Acrylic acid/horse
Carry out anhydride/formula（II-2）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-3）Copolymer,（Methyl）Propylene
Acid/maleic anhydride/formula（II-4）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-5）Copolymer,（Methyl）
Acrylic acid/maleic anhydride/formula（II-6）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-7）Copolymer,（First
Base）Acrylic acid/maleic anhydride/formula（II-8）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-9）Copolymer,
（Methyl）Acrylic acid/maleic anhydride/formula（II-10）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-11）Be total to
Polymers,（Methyl）Acrylic acid/maleic anhydride/formula（II-12）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-
13）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-14）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula
（II-15）Copolymer etc..
As the specific example of polymer ［ A2 ］,（Methyl）Acrylic acid/formula（I-1）/（Methyl）The copolymerization of acrylic acid methyl ester.
Thing,（Methyl）Acrylic acid/formula（I-2）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（I-3）/（First
Base）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（I-4）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Third
Olefin(e) acid/formula（I-5）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（I-6）/（Methyl）Acrylic acid methyl ester.
Copolymer,（Methyl）Acrylic acid/formula（I-7）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（I-
8）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（I-9）/（Methyl）The copolymer of acrylic acid methyl ester.,
（Methyl）Acrylic acid/formula（I-10）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（I-11）/（Methyl）
The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（I-12）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Propylene
Acid/formula（I-13）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（I-14）/（Methyl）Acrylic acid methyl ester.
Copolymer,（Methyl）Acrylic acid/formula（I-15）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-
1）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-2）/（Methyl）The copolymer of acrylic acid methyl ester.,
（Methyl）Acrylic acid/formula（II-3）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-4）/（Methyl）
The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-5）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Propylene
Acid/formula（II-6）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-7）/（Methyl）Acrylic acid methyl ester.
Copolymer,（Methyl）Acrylic acid/formula（II-8）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-
9）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-10）/（Methyl）The copolymer of acrylic acid methyl ester.,
（Methyl）Acrylic acid/formula（II-11）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-12）/（First
Base）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-13）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）
Acrylic acid/formula（II-14）/（Methyl）The copolymer of acrylic acid methyl ester.,（Methyl）Acrylic acid/formula（II-15）/（Methyl）Propylene
The copolymer of sour methyl ester,（Methyl）Acrylic acid/formula（I-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Third
Olefin(e) acid/formula（II-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/formula（I-1）/ formula（II-
1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester .beta.-methylacrylic acid/formula（I-1）/（Methyl）Being total to of acrylic acid bicyclopentyl ester
Polymers, maleic acid/formula（I-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/maleic anhydride/formula
（I-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid methyl ester ./
（Methyl）The copolymer of acrylic acid bicyclopentyl ester .beta.-methylacrylic acid/formula（II-1）/（Methyl）The copolymerization of acrylic acid bicyclopentyl ester
Thing, maleic acid/formula（II-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/maleic anhydride/formula
（II-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/formula（II-1）/（Methyl）Acrylic acid first
Ester/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Phenyl acrylate
Copolymer,（Methyl）Acrylic acid/formula（II-1）/（Methyl）The copolymer of phenyl acrylate,（Methyl）Acrylic acid/formula（I-
1）/ formula（II-1）/（Methyl）The copolymer of phenyl acrylate .beta.-methylacrylic acid/formula（I-1）/（Methyl）Phenyl acrylate
Copolymer, maleic acid/formula（I-1）/（Methyl）The copolymer of phenyl acrylate,（Methyl）Acrylic acid/maleic anhydride/formula
（I-1）/（Methyl）The copolymer of phenyl acrylate,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid methyl ester ./（First
Base）The copolymer of phenyl acrylate .beta.-methylacrylic acid/formula（II-1）/（Methyl）The copolymer of phenyl acrylate, maleic acid/formula
（II-1）/（Methyl）The copolymer of phenyl acrylate,（Methyl）Acrylic acid/maleic anhydride/formula（II-1）/（Methyl）Propylene
The copolymer of sour phenylester,（Methyl）Acrylic acid/formula（II-1）/（Methyl）Acrylic acid methyl ester ./（Methyl）Phenyl acrylate
Copolymer,（Methyl）Acrylic acid/formula（I-1）The copolymer of/ethyl maleate.,（Methyl）Acrylic acid/formula（II-1）/ Malaysia
The copolymer of diethyl phthalate,（Methyl）Acrylic acid/formula（I-1）/ formula（II-1）The copolymer of/ethyl maleate. .beta.-methylacrylic acid/
Formula（I-1）The copolymer of/ethyl maleate., maleic acid/formula（I-1）The copolymer of/ethyl maleate.,（Methyl）Propylene
Acid/maleic anhydride/formula（I-1）The copolymer of/ethyl maleate.,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid
The copolymer of methyl ester/ethyl maleate. .beta.-methylacrylic acid/formula（II-1）The copolymer of/ethyl maleate., maleic acid/formula
（II-1）The copolymer of/ethyl maleate.,（Methyl）Acrylic acid/maleic anhydride/formula（II-1）Being total to of/ethyl maleate.
Polymers,（Methyl）Acrylic acid/formula（II-1）/（Methyl）The copolymer of acrylic acid methyl ester ./ethyl maleate.,（Methyl）Propylene
Acid/formula（I-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/formula（II-1）/（Methyl）Third
The copolymer of olefin(e) acid -2- hydroxy methacrylate,（Methyl）Acrylic acid/formula（I-1）/ formula（II-1）/（Methyl）Acrylic acid -2- hydroxyl
The copolymer of base ethyl ester .beta.-methylacrylic acid/formula（I-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate, maleic acid/formula
（I-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/maleic anhydride/formula（I-1）/（First
Base）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid methyl ester ./（Methyl）
The copolymer of 2-Hydroxy ethyl acrylate .beta.-methylacrylic acid/formula（II-1）/（Methyl）The copolymerization of 2-Hydroxy ethyl acrylate
Thing, maleic acid/formula（II-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/maleic anhydride/
Formula（II-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/formula（II-1）/（Methyl）Propylene
Sour methyl ester/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/formula（I-1）/ bicyclic ［ 2.2.1 ］
The copolymer of hept-2-ene",（Methyl）Acrylic acid/formula（II-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）
Acrylic acid/formula（I-1）/ formula（II-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene" .beta.-methylacrylic acid/formula（I-1）/ bicyclic
2.2.1 ］ the copolymer of hept-2-ene", maleic acid/formula（I-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）Third
Olefin(e) acid/maleic anhydride/formula（I-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）Acrylic acid/formula（I-1）/（First
Base）The copolymer of acrylic acid methyl ester ./bicyclic ［ 2.2.1 ］ hept-2-ene" .beta.-methylacrylic acid/formula（II-1）/ bicyclic ［ 2.2.1 ］ hept-
The copolymer of 2- alkene, maleic acid/formula（II-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）Acrylic acid/Malaysia
Anhydride/formula（II-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）Acrylic acid/formula（II-1）/（Methyl）Propylene
The copolymer of sour methyl ester/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）Acrylic acid/formula（I-1）/ N- N-cyclohexylmaleimide
Copolymer,（Methyl）Acrylic acid/formula（II-1）The copolymer of/N- N-cyclohexylmaleimide,（Methyl）Acrylic acid/formula
（I-1）/ formula（II-1）The copolymer of/N- N-cyclohexylmaleimide .beta.-methylacrylic acid/formula（I-1）/ N- cyclohexyl maleoyl
The copolymer of imines, maleic acid/formula（I-1）The copolymer of/N- N-cyclohexylmaleimide,（Methyl）Acrylic acid/maleic acid
Acid anhydride/formula（I-1）The copolymer of/N- N-cyclohexylmaleimide,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid first
The copolymer of ester/N- N-cyclohexylmaleimide .beta.-methylacrylic acid/formula（II-1）The copolymer of/N- N-cyclohexylmaleimide,
Maleic acid/formula（II-1）The copolymer of/N- N-cyclohexylmaleimide,（Methyl）Acrylic acid/maleic anhydride/formula（II-1）/
The copolymer of N- N-cyclohexylmaleimide,（Methyl）Acrylic acid/formula（II-1）/（Methyl）Acrylic acid methyl ester ./N- cyclohexyl
The copolymer of maleimide,（Methyl）Acrylic acid/formula（I-1）/ cinnamic copolymer,（Methyl）Acrylic acid/formula（II-
1）/ cinnamic copolymer,（Methyl）Acrylic acid/formula（I-1）/ formula（II-1）/ cinnamic copolymer .beta.-methylacrylic acid/formula
（I-1）/ cinnamic copolymer, maleic acid/formula（I-1）/ cinnamic copolymer,（Methyl）Acrylic acid/maleic anhydride/formula
（I-1）/ cinnamic copolymer,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid methyl ester ./cinnamic copolymer,
.beta.-methylacrylic acid/formula（II-1）/ cinnamic copolymer, maleic acid/formula（II-1）/ cinnamic copolymer,（Methyl）Acrylic acid/
Maleic anhydride/formula（II-1）/ cinnamic copolymer,（Methyl）Acrylic acid/formula（II-1）/（Methyl）Acrylic acid methyl ester ./benzene
The copolymer of ethylene,（Methyl）Acrylic acid/formula（I-1）/ N- N-cyclohexylmaleimide/cinnamic copolymer,（Methyl）
Acrylic acid/formula（II-1）/ N- N-cyclohexylmaleimide/cinnamic copolymer,（Methyl）Acrylic acid/formula（I-1）/ formula
（II-1）/ N- N-cyclohexylmaleimide/cinnamic copolymer .beta.-methylacrylic acid/formula（I-1）/ N- cyclohexyl maleimide
Amine/cinnamic copolymer, maleic acid/formula（I-1）/ N- N-cyclohexylmaleimide/cinnamic copolymer,（Methyl）Third
Olefin(e) acid/maleic anhydride/formula（I-1）/ N- N-cyclohexylmaleimide/cinnamic copolymer,（Methyl）Acrylic acid/formula（I-
1）/（Methyl）Acrylic acid methyl ester ./N- N-cyclohexylmaleimide/cinnamic copolymer .beta.-methylacrylic acid/formula（II-1）/ N- ring
Hexyl maleimide/cinnamic copolymer, maleic acid/formula（II-1）/ N- N-cyclohexylmaleimide/cinnamic common
Polymers,（Methyl）Acrylic acid/maleic anhydride/formula（II-1）/ N- N-cyclohexylmaleimide/cinnamic copolymer,（First
Base）Acrylic acid/formula（II-1）/（Methyl）Acrylic acid methyl ester ./N- N-cyclohexylmaleimide/cinnamic copolymer etc..
Polymer（A）Polystyrene conversion weight average molecular weight be preferably 3,000～100,000, more preferably 5,000～
50,000, further preferred 5,000～25,000, particularly preferred 5,000～15,000.Polymer（A）Weight average molecular weight exist
During above range, coating has the tendency of to become good.
Polymer（A）Molecular weight distribution ［ weight average molecular weight（Mw）/ number-average molecular weight（Mn）It is preferably 1.1～6.0, more
Preferably 1.2～4.0.In above range, it is excellent that the film of gained has the tendency of chemical proofing to molecular weight distribution.
Polymer（A）Acid number be preferably 30mg-KOH/g～180mg-KOH/g, more preferably 40mg-KOH/g～
150mg-KOH/g, particularly preferred 50mg-KOH/g～135mg-KOH/g.Wherein, acid number is as neutralizing polymer
The amount of the potassium hydroxide required for 1g（mg）Come the value to measure, titration can be carried out to ask by using potassium hydroxide aqueous solution
?.Polymer（A）Acid number in above range, the excellent tendency of the tack of rewarding film and substrate.
Polymer（A）Content with respect to polymer（A）Content with（Methyl）Acyclic compound（B）Content total
Meter, preferably 30～90 mass %, more preferably 40～80 mass %.Polymer（A）Content in above range, rewarding
Film becomes good tendency with the tack of substrate and chemical proofing.
The hardening resin composition of the present invention preferably comprises at least 1 having selected from acryloyl group and methylacryloyl
Plant group（Hereinafter sometimes referred to "（Methyl）Acryloyl group "）Compound（B）（Hereinafter sometimes referred to "（Methyl）Acrylic acid chemical combination
Thing（B）”）.
As having 1（Methyl）Acryloyl group（Methyl）Acyclic compound（B）, can enumerate with as above-mentioned
（a）、（b）With（c）Cited compound is identical compound, wherein, preferably（Methyl）Esters of acrylic acid.
As having 2（Methyl）Acryloyl group（Methyl）Acyclic compound（B）, 1 can be enumerated, 3-butanediol
Two（Methyl）Acrylate, 1,3 butylene glycol（Methyl）Acrylate, 1,6- hexanediol two（Methyl）Acrylate, ethylene glycol
Two（Methyl）Acrylate, diethylene glycol two（Methyl）Acrylate, neopentyl glycol two（Methyl）Acrylate, 2,2'-ethylenedioxybis(ethanol). two（First
Base）Acrylate, tetraethylene glycol (TEG) two（Methyl）Acrylate, polyethyleneglycol diacrylate, bisphenol-A double（Acryloxy second
Base）Ether, Ethoxylated bisphenol A bis-（Methyl）Acrylate, ethoxylated neopentylglycol two（Methyl）Acrylate, ethoxylation
Neopentyl glycol two（Methyl）Acrylate, 3- methyl pentanediol two（Methyl）Acrylate etc..
As having more than 3（Methyl）Acryloyl group（Methyl）Acyclic compound（B）, trihydroxy methyl can be enumerated
Propane three（Methyl）Acrylate, tetramethylolmethane three（Methyl）Acrylate, three（2- hydroxyethyl）Isocyanuric acid three（Methyl）
Acrylate, ethoxylated trimethylolpropane three（Methyl）Acrylate, propoxylation trimethylolpropane tris（Methyl）Third
Olefin(e) acid ester, tetramethylolmethane four（Methyl）Acrylate, dipentaerythritol five（Methyl）Acrylate, dipentaerythritol six（Methyl）
Acrylate, tripentaerythritol four（Methyl）Acrylate, tripentaerythritol five（Methyl）Acrylate, tripentaerythritol six
（Methyl）Acrylate, tripentaerythritol seven（Methyl）Acrylate, tripentaerythritol eight（Methyl）Acrylate, tetramethylolmethane
Three（Methyl）The reactant of acrylate and anhydride, dipentaerythritol five（Methyl）The reactant of acrylate and anhydride, three seasons
Penta tetrol seven（Methyl）The reactant of acrylate and anhydride, caprolactone modification trimethylolpropane tris（Methyl）Acrylate,
Caprolactone modification tetramethylolmethane three（Methyl）Acrylate, caprolactone modification three（2- hydroxyethyl）Isocyanuric acid three（Methyl）
Acrylate, caprolactone modification tetramethylolmethane four（Methyl）Acrylate, caprolactone modification dipentaerythritol five（Methyl）Propylene
Acid esters, caprolactone modification dipentaerythritol six（Methyl）Acrylate, caprolactone modification tripentaerythritol four（Methyl）Acrylic acid
Ester, caprolactone modification tripentaerythritol five（Methyl）Acrylate, caprolactone modification tripentaerythritol six（Methyl）Acrylate,
Caprolactone modification tripentaerythritol seven（Methyl）Acrylate, caprolactone modification tripentaerythritol eight（Methyl）Acrylate, oneself
Lactone-modified tetramethylolmethane three（Methyl）The reactant of acrylate and anhydride, caprolactone modification dipentaerythritol five（Methyl）Third
The reactant of olefin(e) acid ester and anhydride, caprolactone modification tripentaerythritol seven（Methyl）Reactant of acrylate and anhydride etc..
As（Methyl）Acyclic compound（B）, preferably there are more than 3（Methyl）Acryloyl group（Methyl）Propylene
Acid compound（B）, more preferably dipentaerythritol six（Methyl）Acrylate.
（Methyl）Acyclic compound（B）Content with respect to polymer（A）100 mass parts, preferably 10～233 mass
Part, more preferably 25～150 mass parts.（Methyl）Acyclic compound（B）Content in above range, rewarding film
Flatness, reliability and mechanical strength become good tendency.
The hardening resin composition of the present invention preferably comprises polymerization initiator（C）.As polymerization initiator（C）As long as,
It is light, the effect of heat to can be utilized causing（Methyl）Acyclic compound（B）Polymerization compound, particularly do not limit
Fixed, it is possible to use known polymerization initiator.
Polymerization initiator（C）Such as alkyl phenones compound, united imidazole, triaizine compounds, acyl group can be enumerated
Phosphine oxide compound, oxime compound.
Wherein, preferably comprise at least one in united imidazole, alkyl phenones compound and oxime compound
Polymerization initiator, especially, at least one polymerization more preferably containing in oxime compound and united imidazole is drawn
Send out agent.If these polymerization initiators, then especially have the tendency of to form high sensitivity, be therefore preferred.
Above-mentioned alkyl phenones compound be with Alpha-hydroxy alkyl phenones, alpha-alkoxy base alkyl phenones or α-（N-
Substituted-amino）Alkyl phenones, as the compound of part-structure, specifically, can enumerate diethoxy acetyl benzophenone, 2- hydroxyl
Base -2- methyl isophthalic acid-phenyl-propane -1- ketone, benzyl dimethyl ketal, 2- hydroxyl -1- (4-（2- '-hydroxyethoxy
Base）Phenyl) -2- methylpropane -1- ketone, 2- hydroxyl -1- { 4- ［ 4-（2- hydroxy-2-methyl-propiono）-
Benzyl ］-phenyl -2- methyl-propan -1- ketone, 1- hydroxycyclohexylphenylketone, 2- methyl isophthalic acid -（4- methylbenzene
Sulfenyl）- 2- morpholino propane -1- ketone, 2- benzyl -2- dimethylamino -1-（4- morphlinophenyl）Butane-
1- ketone, 2-（2- methyl-benzyl）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（3- methyl benzyl
Base）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（4- methyl-benzyl）- 2- dimethylamino-
1-（4- morphlinophenyl）Butanone, 2-（2- Ethylbenzyl）- 2- dimethylamino -1-（4- morphlinophenyl）Fourth
Ketone, 2-（2- benzyl）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（2- butyl benzyl）-
2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（2,3- dimethyl benzyls）- 2- dimethylamino-
1-（4- morphlinophenyl）Butanone, 2-（2nd, 4- dimethyl benzyl）- 2- dimethylamino -1-（4- morpholino benzene
Base）Butanone, 2-（2- chlorobenzyl）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（2- bromobenzyl
Base）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（3- chlorobenzyl）- 2- dimethylamino -1-
（4- morphlinophenyl）Butanone, 2-（4- chlorobenzyl）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-
（3- bromobenzyl）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（4- bromobenzyl）- 2- dimethyl
Amino -1-（4- morphlinophenyl）Butanone, 2-（2- methoxy-benzyl）- 2- dimethylamino -1-（4- morpholino
Phenyl）Butanone, 2-（3- methoxy-benzyl）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（4- first
Oxy-benzyl）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（2- methyl -4- methoxybenzyl
Base）- 2- dimethylamino -1-（4- morphlinophenyl）Butanone, 2-（2- methyl -4- bromobenzyl）- 2- dimethyl
Amino -1-（4- morphlinophenyl）Butanone, 2-（2- bromo- 4- methoxy-benzyl）- 2- dimethylamino -1-
（4- morphlinophenyl）Butanone, 2- hydroxy-2-methyl -1- (4-（1- methyl ethylene）Phenyl propane -1- ketone
Oligomer, 2-（Dimethylamino）- 2-（4- aminomethyl phenyl）Methyl ］ -1- ［ 4-（4- morpholinyl）Phenyl ］ fourth
Alkane -1- ketone etc..
As above-mentioned oxime compound, N- benzoyloxy -1- can be enumerated（4- Phenylsulfanyl phenyl）Fourth
Alkane-1- ketone-2- imines, N- ethoxy carbonyl Oxy-1-phenyl-propane-1- ketone-2- imines, N- benzoxy
Base -1-（4- Phenylsulfanyl phenyl）Octane -1- ketone -2- imines, N- acetoxyl group -1- ［ 9- ethyl -6-
（2- methyl benzoyl）- 9H- carbazole -3- base ］ ethane -1- imines, N- acetoxyl group -1- 9- ethyl -
6- { 2- methyl -4-（3,3- dimethyl -2,4- dioxolyl methyl epoxide）Benzoyl } -9H- carbazole -
3- yl ］ ethane -1- imines etc..イ Le ガ キ ュ ア OXE01, OXE02 can also be used（More than, BASF society system）, N-
1919（ADEKA society system）Deng commercially available product.
Above-mentioned united imidazole can enumerate 2,2 '-and bis-（2- chlorphenyl）- 4,4 ', 5,5 '-tetraphenyl joins miaow
Azoles, 2,2 '-bis-（2,3- Dichlorobenzene base）- 4,4 ', 5,5 '-tetraphenyl bisglyoxaline（See, for example Japanese Unexamined Patent Publication 6-
No. 75372 publications, Japanese Unexamined Patent Publication 6-75373 publications etc.）, 2,2 '-bis-（2- chlorphenyl）- 4,4 ', 5,5 '-four benzene
Base bisglyoxaline, 2,2 '-bis-（2- chlorphenyl）- 4,4 ', 5,5 '-four（Alkoxyl phenyl）Bisglyoxaline, 2,2 '-bis-（2- chlorine
Phenyl）- 4,4 ', 5,5 '-four（Dialkoxy phenyl）Bisglyoxaline, 2,2 '-bis-（2- chlorphenyl）- 4,4 ', 5,5 '-four
（Tri-alkoxy phenyl）Bisglyoxaline（See, for example Japanese Patent Publication 48-38403 publication, Japanese Unexamined Patent Application No. 62-174204 number
Publication etc.）, 4,4 ' 5, the imidazolium compoundss that the phenyl of 5 '-position is replaced by alkoxy carbonyl group（See, for example Japanese Unexamined Patent Publication 7-
No. 10913 publications etc.）Deng.Can preferably enumerate 2,2 '-bis-（2- chlorphenyl）- 4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,
2 '-bis-（2nd, 3- Dichlorobenzene base）- 4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-（2nd, 4- Dichlorobenzene base）- 4,4 ',
5,5 '-tetraphenyl bisglyoxaline.
It is double that above-mentioned triaizine compounds can enumerate 2,4-（Trichloromethyl）- 6-（4- methoxyphenyl）- 1,3,
5- triazine, 2,4- are double（Trichloromethyl）- 6-（4- methoxyl group naphthyl）- 1,3,5-triazines, 2,4- are double（Three chloromethanes
Base）- 6- piperonyl -1,3,5-triazines, 2,4- are double（Trichloromethyl）- 6- (4- methoxyl-styrene) -1,3,
5- triazine, 2,4- are double（Trichloromethyl）- 6- (2-（5- methylfuran -2- base）Vinyl) -1,3,5-triazines, 2,
4- is double（Trichloromethyl）- 6- (2-（Furan -2- base）Vinyl) -1,3,5-triazines, 2,4- be double（Trichloromethyl）-
6- (2-（4- diethylamino -2- aminomethyl phenyl）Vinyl) -1,3,5-triazines, 2,4- be double（Trichloromethyl）-
6- (2-（3,4- Dimethoxyphenyls）Vinyl) -1,3,5-triazines etc..
Above-mentioned acylphosphine oxide compound can enumerate TMDPO etc..
Further, as polymerization initiator（C）, Benzoinum, benzoin methyl ether, benzoin ethyl ether can be enumerated, rest in peace
The aroma compounds of resting in peace of fragrant diisopropyl ether, benzoin isobutyl ether etc.；Benzophenone, o-benzoyl yl benzoic acid methyl ester, 4- phenyl two
Benzophenone, 4- benzoyl -4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four（Tert-butyl hydroperoxide carbonyl）Hexichol first
The benzophenone cpd of ketone, 2,4,6- tri-methyl benzophenones etc.；9,10- phenanthrenequione, 2-ethyl-anthraquinone, camphorquinone etc.
Naphtoquinone compounds；10- butyl -2- chloro-acridine ketone, dibenzoyl, phenylglyoxalates methyl ester, titanocenes compound etc..They are excellent
Choosing is polymerized initiation auxiliary agent with following（C1）It is applied in combination.
Alternatively, it is also possible to using described in Japanese Unexamined Patent Application Publication 2002-544205 publication, have and can cause chain tra nsfer
Group polymerization initiator.
In the hardening resin composition of the present invention, it is possible to further with above-mentioned polymerization initiator（C）Come together to make
Cause auxiliary agent with polymerization（C1）.Polymerization causes auxiliary agent（C1）Can be with polymerization initiator（C）It is applied in combination, it is for promoting by gathering
Close the compound of the polymerization of polymerizable compound or the sensitizer that initiator causes polymerization.Polymerization causes auxiliary agent（C1）Can arrange
Lift thioxanthone compounds, thiazolinium compounds, alkoxy anthracene compound, amines and carboxylic acid compound etc..By by they
With polymerization initiator（C）Combination, can obtain pattern with high sensitivity.
Thioxanthone compounds can enumerate ITX, ITX, 2,4- diethyl thioxanthene
Ketone, 2,4- bis- clopenthixal ketone, 1- chloro- 4- propoxythioxanthone etc..
Thiazolinium compounds can be with enumerative（III-1）～formula（III-3）Shown compound, Japanese Unexamined Patent Publication 2008-
Compound of No. 65319 publication records etc..
【Change 7】
Alkoxy anthracene compound can enumerate 9,10- dimethoxy anthracene, EDMO, 9,
10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene, 9,10- dibutoxy anthracene, 2- ethyl -9,10- bis- fourth
Compound that epoxide anthracene, Japanese Unexamined Patent Publication 2009-139932 publication are recorded etc..
Amines can enumerate triethanolamine, methyl diethanolamine, triisopropanolamine etc. aliphatic amine compound,
4- dimethylaminobenzoic acid methyl ester, EDMAB, 4- dimethylaminobenzoic acid isopentyl ester, 4-
Dimethylaminobenzoic acid 2- Octyl Nitrite, benzoic acid 2- dimethylamino ethyl ester, N, N- dimethyl-p-toluidine, 4,
4 '-bis-（Dimethylamino）Benzophenone（Common name；ミヒラーズケトン）, 4,4 '-bis-（Diethylamino）Benzophenone
Such aromatic amines compound.
Carboxylic acid compound can enumerate Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, ethylphenyl sulfanyl second
Acid, Methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfane guanidine-acetic acid, dimethoxy
Phenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, Dichlorobenzene base sulfane guanidine-acetic acid, N-phenylglycine, phenoxyacetic acid,
The aromatic series miscellaneous acetic acid class of naphthylthio acetic acid, N- naphthyl glycine, naphthoxy acetic acid etc..
Polymerization initiator（C）Content with respect to polymer（A）With（Methyl）Acyclic compound（B）Total 100 matter
Amount part, preferably 0.5～30 mass parts, more preferably 1～20 mass parts, further preferred 2～10 mass parts.Polymerization initiator
（C）Content in above range, have the tendency of to obtain pattern with high sensitivity, be preferred.
Polymerization causes auxiliary agent（C1）Usage amount with respect to resin（A）With（Methyl）Acyclic compound（B）Total 100
Mass parts, preferably 0.1～10 mass parts, more preferably 0.3～7 mass parts.Polymerization causes auxiliary agent（C1）Amount in above range
When, pattern can be obtained with high sensitivity, the shape of the pattern of gained is good, from but preferably.
The hardening resin composition of the present invention contains following formula（1）Shown imidazolium compoundss（Hereinafter sometimes referred to " imidazoles
Compound（D）”）.
【Change 8】
(formula（1）In, R1Expression benzyl or the cyanoalkyl that carbon number is 2～5.
R2～R4Represent independently of each other alkyl, phenyl, nitro that hydrogen atom, halogen atom, carbon number are 1～20 or
Carbon number is 1～20 acyl group, and the hydrogen atom containing in this alkyl and this phenyl can be optionally substituted by a hydroxyl group.〕
Carbon number be 1～20 alkyl can enumerate for example methyl, ethyl, propyl group, isobutyl group, butyl, the tert-butyl group, oneself
Base, heptyl, octyl group, nonyl, decyl, heptadecyl, undecyl etc., preferably carbon number are 1～15, more preferably carbon number
For 1～12.
The cyanoalkyl being 2～5 as carbon number, can enumerate cyano methyl, cyano ethyl, cyanopropyl, cyano group
Butyl, cyanopentyl etc..
Halogen atom can enumerate such as fluorine atom, chlorine atom, bromine atoms etc..
Carbon number is that 1～20 acyl group can enumerate such as formoxyl, acetyl group, propiono, isobutyryl, valeryl
Base, isovaleryl, pivaloyl group, lauroyl, tetradecanoyl and octadecanoyl etc..
R2Preferably it is independently of one another the alkyl or phenyl that hydrogen atom, carbon number are 1～20, in this alkyl and this phenyl
The hydrogen atom containing can be optionally substituted by a hydroxyl group, and more preferably hydrogen atom, carbon number are 1～20 alkyl or phenyl, excellent further
Choosing is the alkyl or phenyl that carbon number is 1～20.
R3And R4Preferably it is independently of one another alkyl or phenyl, this alkyl and this benzene that hydrogen atom, carbon number are 1～20
The hydrogen atom containing in base can be optionally substituted by a hydroxyl group, and more preferably hydrogen atom, carbon number are 1～20 alkyl or phenyl, enter one
Step is preferably hydrogen atom or alkyl that carbon number is 1～10, particularly preferably hydrogen atom or alkyl that carbon number is 1～6.
Imidazolium compoundss（D）Can enumerate such as 1- benzyl -4-methylimidazole, 1- benzyl -4-methylimidazole,
1- benzyl -4- phenylimidazole, 1- benzyl -5- hydroxymethylimidazole, 1- cyano methyl -2-methylimidazole, 1-
（2- cyano ethyl）- 2- hydroxymethylimidazole, 1- cyano methyl -2- undecyl imidazole, 1- cyano methyl -2-
Ethyl -4-methylimidazole, 1- cyano methyl -2- phenylimidazole, 1-（2- cyano ethyl）- 2- ethyl -4- methyl
Imidazoles etc..Wherein preferred 1- benzyl -4- phenylimidazole, 1-（2- cyano ethyl）- 2-ethyl-4-methylimidazole.It
Can be used alone, or two or more is applied in combination.
Imidazolium compoundss（D）Content with respect to polymer（A）100 mass parts, preferably 1 mass parts～25 mass parts,
More preferably 1.5 mass parts～20 mass parts.Imidazolium compoundss（D）Content in above range, rewarding pattern or film
The excellent tendency of the transparency.
The hardening resin composition of the present invention preferably further contains mercaptan compound（T）.Mercaptan compound（T）Be
Intramolecular has sulfanyl（- SH）Compound.Wherein, preferably there is the compound of more than 2 sulfanyls, more preferably have 2
The compound of the sulfanyl of carbon atom bonding of individual above and aliphatic hydrocarbon structures.By the curable resin combination in the present invention
Mercaptan compound is contained in thing（T）, have the tendency of sensitivity and uprise.
Mercaptan compound（T）Such as ethanthiol, the last of the ten Heavenly stems two mercaptan, Isosorbide-5-Nitrae-bis- can be enumerated（Methylsulfanyl）Benzene, fourth two
Alcohol is double（3- sulfanyl propionic ester）, butanediol double（3- sulfane yl acetate）, ethylene glycol double（3- sulfane yl acetate）, three
Hydroxymethyl-propane three（3- sulfane yl acetate）, butanediol double（3- sulfanyl propionic ester）, trimethylolpropane tris（3- sulfur
Alkyl propionate）, trimethylolpropane tris（3- sulfane yl acetate）, tetramethylolmethane four（3- sulfanyl propionic ester）, season penta
Tetrol four（3- sulfane yl acetate）, trihydroxy ethyl three（3- sulfanyl propionic ester）, tetramethylolmethane four（3- sulfanyl fourth
Acid esters）, Isosorbide-5-Nitrae-bis-（3- sulfanyl butyl epoxide）Butane etc..
Mercaptan compound（T）Content with respect to polymerization initiator（C）100 mass parts, preferably 10～90 mass parts, more
Preferably 15～70 mass parts.Work as mercaptan compound（T）Content in this scope, sensitivity uprises, and in addition developability has becomes good
Good tendency.
The hardening resin composition of the present invention preferably comprises solvent（E）.
Solvent（E）It is not particularly limited, it is possible to use the solvent being usually used in this field.Can be for example from ester solvent
（Intramolecular contains-COO-, the solvent without-O-）, ether solvents（Intramolecular contains-O-, does not contain the molten of-COO-
Agent）, ether-ether solvent（Intramolecular contains the solvent of-COO- and-O-）, ketone solvent（Intramolecular contain-CO-, do not contain-
The solvent of COO-）, alcoholic solvent（Intramolecular contains OH, the solvent without-O- ,-CO- and-COO-）, aromatic hydrocarbon molten
Select in agent, amide solvent, dimethyl sulfoxide etc. to use.
Ester solvent can enumerate methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acid, ethyl acetate,
N-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl n-butyrate., butanoic acid fourth
Ester, methyl pyruvate, ethyl pyruvate, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate,
Gamma-butyrolacton etc..
Ether solvents can enumerate ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol only son
Base ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monobutyl ehter, propylene glycol monomethyl ether, propylene glycol list ethyl
Ether, propylene glycol monopropyl ether, glycol monobutyl ether, 3- methoxyl group-n-butyl alcohol, 3- methoxyl group -3- methyl butanol, four
Hydrogen furan, Pentamethylene oxide., Isosorbide-5-Nitrae-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, two
Glycol dipropyl ether, diethylene glycol dibutyl ether, methoxybenzene, ethyl phenyl ether, methyl anisole etc..
Ether-ether solvent can enumerate methoxy menthyl acetate, ethyl methoxyacetate, 2-Methoxyacetic acid butyl ester, ethyoxyl second
Sour methyl ester, ethoxy ethyl acetate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxypropanoate,
3- ethoxyl ethyl propionate, 2- methoxy methyl propionate, 2- methoxypropionate, 2- methoxy propyl propyl propionate, 2- second
Epoxide methyl propionate, 2- ethoxyl ethyl propionate, 2- methoxyl group -2 Methylpropionic acid methyl ester, 2- ethyoxyl -2- methyl
Ethyl propionate, 3- methoxybutyl acetass, 3- methyl -3- methoxybutyl acetass, propylene glycol monomethyl ether
Ester, propylene glycol monoethyl acetass, propylene glycol monopropyl ether acetass, ethylene glycol single methyl ether acetass, ethylene glycol list second
Base ether acetic acid ester, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ehter acetass etc..
Ketone solvent can enumerate 4- hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3- heptanone,
Dipropyl ketone, 4-methyl-2 pentanone, Ketocyclopentane, Ketohexamethylene, isophorone etc..
Alcoholic solvent can enumerate methanol, ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol, glycerol etc..
Aromatic hydrocarbon solvents can enumerate benzene,toluene,xylene, sym-trimethylbenzene. etc..
Amide solvent can enumerate DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone
Deng.
These solvents may be used alone, or two or more kinds may be used in combination.
In above-mentioned solvent, from the point of view of coating, drying property, the boiling point under preferably 1atm is 120 DEG C～180 DEG C
Organic solvent.Wherein, preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether,
3- methoxybutyl acetass, 3- methoxyl group-n-butyl alcohol and the mixed solvent containing them.
Solvent in hardening resin composition（E）Content with respect to hardening resin composition, preferably 60～95
Quality %, more preferably 70～95 mass %.In other words, the solid composition of hardening resin composition is preferably 5～40 matter
Amount %, more preferably 5～30 mass %.Wherein, solid composition refers to eliminate solvent from hardening resin composition（E）'s
Amount.Solvent（E）Content in above range, be coated with the film of hardening resin composition flatness have the tendency of high.
The hardening resin composition of the present invention preferably comprises antioxidant（F）.Antioxidant（F）Can enumerate for example
The 2- tert-butyl group -6-（The 3- tert-butyl group -2- hydroxy-5-methyl base benzyl）- 4- aminomethyl phenyl acrylate, 2- ［ 1-
（2- hydroxyl -3,5- di-tert-pentyl-phenyl）Ethyl ］ -4,6- di-tert-pentyl-phenyl acrylate, 6- ［ 3-（The tertiary fourth of 3-
Base -4- hydroxy-5-methyl base phenyl）Propoxyl group ］ -2,4,8,10- tetra-tert dibenzo ［ d, f ］ ［ 1,3,2 ］ dioxas
Double ［ 2- { the 3- of phospha cycloheptene, 3,9-（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl）Propionyloxy } -1,1- bis-
Methylethyl ］ -2,4,8,10- tetra- oxaspiro ［ 5.5 ］ hendecanes, 2,2 '-di-2-ethylhexylphosphine oxide（The 6- tert-butyl group -4- methyl
Phenol）, 4,4 '-butylidene is double（The 6- tert-butyl group -3- methylphenol）, 4,4 '-thiobiss（The 2- tert-butyl group -5- methyl
Phenol）, 2,2 '-thiobiss（6- tert-butyl-4-methyl-Phenol）, 3,3 '-thio-2 acid two（Dodecyl）Ester, 3,
3 '-thio-2 acid two（Myristyl）Ester, 3,3 '-thio-2 acid two（Octadecyl）Ester, tetramethylolmethane four（3- ten
Dialkyl propionic ester）, 1,3,5- tri-（3,5- di-tert-butyl-4-hydroxyl benzyls）- 1,3,5-triazines -2,4,6
（1H, 3H, 5H）- triketone, 3,3 ', 3 ", 5,5 ', 5 "-six tert-butyl group-a, a ', a "-（Sym-trimethylbenzene. -2,4,6- tri- bases）
Three-paracresol, tetramethylolmethane four ［ 3-（3,5- di-tert-butyl-hydroxy phenyls）Propionic ester ］, 2,6- di-t-butyl-
4- methylphenol etc..IRGANOX can be used（Registered trade mark）3114（BASF ジ ャ パ Application society system）Deng commercially available product.
Antioxidant（F）Content with respect to polymer（A）100 mass parts, are 0.1 mass parts～5 mass parts, preferably
0.5 mass parts～3 mass parts.Antioxidant（F）Content within the above range when, the film of gained has thermostability and pencil hard
Spend excellent tendency.Antioxidant（F）Content more than during 5 mass parts it is possible to pencil hardness reduce.
The hardening resin composition of the present invention can contain surfactant（G）.Surfactant can be enumerated for example
Silicone type surface active agent, fluorine system surfactant, there is silicone type surface active agent of fluorine atom etc..
Silicone type surface active agent can enumerate the surfactant with siloxanes key.Specifically, ト can be enumerated
レ シ リ U Application DC3PA, ibid SH7PA, ibid DC11PA, ibid SH21PA, ibid SH28PA, ibid SH29PA, ibid
SH30PA, polyether modified silicon oil SH8400（Trade name：Eastern レ ダ ウ conning（Strain）System）、KP321、KP322、
KP323、KP324、KP326、KP340、KP341（SHIN-ETSU HANTOTAI's chemical industry（Strain）System）、TSF400、TSF401、TSF410、
TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460（モメンティブ・パフォーマンス・
マ テ リ ア Le ズ ジ ャ パ Application contract commercial firm system）Deng.
Fluorine system surfactant can be enumerated with fluorocarbon chain（Off Le オ ロ カ ボ Application）Surfactant.
Specifically, Off ロ リ Na ト can be enumerated（Registered trade mark）FC430, ibid FC431（Sumitomo ス リ エ system（Strain）
System）；メガファック（Registered trade mark）F142D, ibid F171, ibid F172, ibid F173, ibid F177, ibid F183,
Ibid F552, ibid F553, ibid F554, ibid F555, ibid F556, ibid F558, ibid F559, ibid R30（DIC
（Strain）System）；エフトップ（Registered trade mark）EF301, ibid EF303, ibid EF351, ibid EF352（Rhizoma Sparganii マ テ リ ア Le electricity
Son chemical conversion（Strain）System）；サーフロン（Registered trade mark）S381, ibid S382, ibid SC101, ibid SC105（Asahi Glass
（Strain）System）；E5844（（Strain）The research of ダ イ キ Application Off ァ イ Application ケ ミ カ Le is made）Deng.
As the silicone type surface active agent with fluorine atom, the surface with siloxanes key and fluorocarbon chain can be enumerated
Activating agent.Specifically, メ ガ Off ァ ッ Network can be enumerated（Registered trade mark）R08, ibid BL20, ibid F475, ibid F477, with
Upper F443（DIC（Strain）System）Deng.Preferably enumerate メ ガ Off ァ ッ Network（Registered trade mark）F475.
Surfactant（G）With respect to hardening resin composition, it is 0.001 mass %～0.2 mass %, preferably
0.002 mass %～0.1 mass %, more preferably 0.01 mass %～0.05 mass %.Lived by surface is contained with this scope
Property agent, can make the flatness of film good.
As needed, can contain in the hardening resin composition of the present invention filler, other macromolecular compound,
The additive of hot radical producing agent, UV absorbent, chain-transferring agent, adhesion promoter etc..
Filler can enumerate glass, silicon dioxide, aluminium oxide etc..
As other macromolecular compounds, the heat-curing resin of maleimide resin etc. or poly- second can be enumerated
Thermoplastic resin of enol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester, polyurethane etc. etc..
Hot radical producing agent specifically can enumerate 2, and 2 '-azo is double（2- methyl valeronitrile）, 2,2 '-azo is double（2,
4- methyl pentane nitrile）Deng.
UV absorbent specifically, can enumerate 2-（The 3- tert-butyl group -2- hydroxy-5-methyl base phenyl）-
5- chlorobenzotriazole, alkoxy benzophenone etc..
Chain-transferring agent can enumerate lauryl mercaptan, 2,4- diphenyl -4-methyl-1-pentene etc..
Adhesion promoter can enumerate such as vinyltrimethoxy silane, VTES, vinyl
Three（2- methoxy ethoxy）Silane, 3- glycidyloxypropyl trimethoxy silane, 3- glycidoxypropyl
Dimethoxysilane, 3- glycidoxypropyl dimethoxysilane, 3- glycidoxypropyl diethoxy silane,
2-（3,4- epoxycyclohexyls）Ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilane, 3- chloropropyl front three
TMOS, 3- methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane, 3- sulfanyl
Propyl trimethoxy silicane, 3- NCO propyl-triethoxysilicane, N-2-（Amino-ethyl）- 3- aminopropyl
Methyl dimethoxysilane, N-2-（Amino-ethyl）- 3-amino propyl methyl diethoxy silane, N-2-（Amino second
Base）- 3- TSL 8330, N-2-（Amino-ethyl）- 3-amino propyl methyl diethoxy silane,
3- TSL 8330, APTES, N- phenyl -3- aminopropyl trimethoxy
Silane, N- phenyl-APTES etc..
In addition, the hardening resin composition of the present invention contains substantially no the coloring agent of pigment and dyestuff etc..That is, at this
In the hardening resin composition of invention, coloring agent is for example, less than 1 mass % with respect to the content of all compositions, preferably little
In 0.5 mass %.
In addition, the hardening resin composition of the present invention is filled in the quartz cell that light path is 1cm, using spectrophotometric
When measuring mensure transmission coefficient under conditions of wavelength is 400～700nm, average transmission coefficient is preferably more than 70% to meter, more
It is preferably more than 80%.
The hardening resin composition of the present invention when being formed as film, the average transmission coefficient of film be preferably 90% with
On, more preferably more than 95%.This average transmission coefficient is for being heating and curing（Such as 100～250 DEG C, 5 minutes～3 hours）Afterwards
Thickness be 3 μm of film, measuring meansigma methodss when measuring under conditions of wavelength is 400～700nm using spectrophotometer.
Thus, it is possible to provide the transparency in visible region excellent film.
The hardening resin composition of the present invention can be using existing known method by polymer（A）、（Methyl）Propylene
Acid compound（B）, polymerization initiator（C）And imidazolium compoundss（D）, solvent as needed or other additive etc. stirred
Mix mixing to manufacture.After mixing, the filter being 0.05～1.0 μm about preferably by aperture is filtered.
The hardening resin composition of the present invention passes through to be coated on the such as substrate of glass, metal, plastics etc., forms colour filter
On these substrates of device, various insulation or conducting film, drive circuit etc., can be formed as film.Film is preferably by
Be dried and solidification film.In addition, by being patterned the film of gained, and form desired shape, can conduct
Pattern is using.It is possible to further these films or pattern are formed as display device etc. component parts a part and
Use.
First, the hardening resin composition of the present invention is coated on substrate.
Coating is as set forth above, it is possible to use spin coater, slit ＆ spin coater, slit coater, ink discharge device（イン
クジェット）, roll coater, the various apparatus for coating of dip coater etc. to be carrying out.
Then, preferably it is dried or preliminary drying, remove the volatile ingredient of solvent etc..Thus, it is possible to obtain smooth not consolidating
Change film.
The thickness of film now is not particularly limited, and suitably can be adjusted according to material used, purposes etc., can
To enumerate such as 1～6 μm about.
Further, for the uncured film of gained, by the mask for forming purpose pattern, irradiation light, such as
Ultraviolet being produced by finsen lamp, light emitting diode etc..The shape of mask now is not particularly limited, and can enumerate various
Shape.As long as in addition, the transmission coefficient of mask transmittance section can pass through the transmission coefficient of the light from light source, not especially
Restriction.The width of pattern, height etc. suitably can be adjusted by mask size, transmission coefficient of mask transmittance section etc..
Can be using exposure machine in recent years, the wave filter that the light less than 350nm, use can be filtered this wavelength domain is carried out
Filter, or by 436nm nearby, the light neighbouring, near 365nm of 408nm, use can obtain the band filter of these wavelength domains
Optionally obtained, equably irradiation parallel rayies overall to plane of exposure.Now correct with substrate in order to be masked
The be aligned of position, it is possible to use the device of mask aligner, stepper etc..
Then, so that film is contacted with alkaline aqueous solution, make established part, the dissolving of such as non-exposed portion, development, thus permissible
Obtain the pattern form as purpose.
Developing method can be that method is put in leaching（Liquid contains り method）, infusion process, any means of nebulization etc..Further, aobvious
Substrate can be made during shadow to be inclined to arbitrary angle.
Used in development, developer solution is preferably the aqueous solution of alkali compoundss.
Alkali compoundss can be any one of inorganic and organic alkali compoundss.
The specific example of inorganic alkaline compound can enumerate sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, biphosphate
Sodium, diammonium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, carbonic acid
Hydrogen potassium, sodium borate, potassium borate, ammonia etc..
In addition, as organic basic compound, such as Tetramethylammonium hydroxide, 2- hydroxyethyl trimethyl can be enumerated
Ammonium hydroxide, MMA, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single 2-aminopropane., diisopropylamine, ethanolamine
Deng.
These are inorganic and organic basic compound concentration in aqueous is preferably 0.01～10 mass %, more preferably
0.03～5 mass %.
The aqueous solution of above-mentioned alkali compoundss can contain surfactant.
Surfactant can be lived in nonionic surfactants, anion system surfactant or cation system surface
Any one of property agent.
Nonionic surfactants can enumerate such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene
Alkyl aryl ether, other polyoxyethylene deriv, ethylene oxide/propylene oxide block copolymer, sorbitol anhydride fatty acid
Ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene
Fatty acid ester, polyoxyethylene alkyl amine etc..
Anion system surfactant can enumerate the higher alcohol sulfur of such as sodium lauryl sulfate, oleyl sulfate sodium etc.
The alkylsurfuric acid salt of acid esters salt, sodium lauryl sulphate or ammonium lauryl sulfate etc., dodecylbenzene sodium sulfonate or ten
Alkylaryl sulfonatess class of dialkyl napthalene sulfonic acids sodium etc. etc..
Cation system surfactant can enumerate the amine of such as 18-amine. hydrochlorate, Dodecyl trimethyl ammonium chloride etc.
Salt or quaternary ammonium salt etc..
The scope of the concentration of the surfactant in alkaline-based developer preferably 0.01～10 mass %, more preferably 0.05～
8 mass %, further preferred 0.1～5 mass %.
After development, washed, after bake can be carried out further as needed.After bake is preferably at such as 150～240 DEG C
Temperature range carries out 10～180 minutes.
The film so obtaining or pattern are as thing optically isolated for example used in liquid crystal indicator（フォトスペ
ーサ）, the cover layer of pattern can be formed（オーバーコート）It is useful.In addition, pattern exposure is being carried out to uncured film
Light time, by using hole formation photomask, hole can be formed, be useful as interlayer dielectric.Further, to not
When cured coating film is exposed, do not use photomask, and carry out entire surface exposure and be heating and curing or be only heating and curing,
Hyaline membrane thus can be formed.This hyaline membrane is useful as cover layer.Alternatively, it is also possible to the display dress in touch panel etc.
Put middle use.Thereby, it is possible to the film of high-quality or the display device of pattern are had with high yield rate manufacture.
The hardening resin composition of the present invention is suitable as the material for forming various films and pattern, for example, be suitable for using
Constitute color filter and/or array base palte in being formed（ア レ イ substrate）The hyaline membrane of a part, pattern, optically isolated thing, covering
Layer, dielectric film, liquid crystal aligning control uses projection, microlens, coating etc..Furthermore it is possible to be used for that there is these films or pattern
As in the color filter of a part for its component parts, array base palte etc., and then can be used for that there is these color filters and/or battle array
In the display device of row substrate etc., such as liquid crystal indicator, organic el device, Electronic Paper etc..
Embodiment
Hereinafter, the present invention is illustrated in more detail by embodiment.Example in " % " and " part " unless otherwise specified,
It is all quality % and mass parts.
（Synthesis example 1）
In the flask with reflux condenser, Dropping funnel and blender, nitrogen is flowed into 0.02L/ minute, form nitrogen
Atmosphere, loads 140 parts of diethylene glycol ethyl-methyl ether, stirs and be heated to 70 DEG C.Then modulation makes 40 parts of methacrylic acid；
And monomer（I-1）And monomer（II-1）The mixture { monomer in mixture（I-1）：Monomer（II-1）Mol ratio
=50：50 } 360 parts, the solution being dissolved in 190 parts of diethylene glycol ethyl-methyl ether, should with 4 hours using Dropping funnel
Solution is added drop-wise in the flask of 70 DEG C of insulations.
【Change 9】
On the other hand, make polymerization initiator 2,2 '-azo is double（2,4- methyl pentane nitriles）30 parts are dissolved in diethylene glycol second
Form solution in 240 parts of ylmethyl ether, with 5 hours, this solution is added drop-wise in flask using other dropping liquid pump.Polymerization is drawn
After sending out the completion of dropwise addition of agent solution, keep 4 hours at 70 DEG C, be subsequently cooled to room temperature, obtaining solid composition is 42.3% be total to
Polymers（Resin A a）Solution.The weight average molecular weight of Resin A a of gained（Mw）For 8000, molecular weight distribution（Mw/Mn）For
1.91, acid number is 60mg-KOH/g（The acid number of solid composition conversion）.
（Synthesis example 2）
In the flask with reflux condenser, Dropping funnel and blender, nitrogen is flowed into 0.02L/ minute, form nitrogen
Atmosphere, adds 3- methoxyl group -200 parts of n-butyl alcohol and 105 parts of 3- methoxybutyl acetass, stirs and be heated to 70
℃.Then, by 60 parts of methacrylic acid, 3,4- epoxy three ring ［ 5.2.1.02.6 ］ decyl acrylate（Formula（I-1）Shown
Compound and formula（II-1）Shown compound, mol ratio are 50：50 mixture.）240 parts are dissolved in 3- methoxyl group fourth
In 140 parts of yl acetate, prepare solution, with 4 hours, this lysate is added drop-wise to the flask being incubated at 70 DEG C using Dropping funnel
Interior.On the other hand, by polymerization initiator 2,2 '-azo is double（2,4- methyl pentane nitriles）30 parts are dissolved in 3- methoxybutyl
Form solution in 225 parts of acetass, by this solution with other Dropping funnel, spend be added drop-wise in flask within 4 hours.Draw in polymerization
Send out agent the completion of dropwise addition of solution after, 70 DEG C keep 4 hours, be subsequently cooled to room temperature, obtain solid composition be 32.6%,
Acid number is 110mg-KOH/g（Solid composition converts）Copolymer（Resin A b）Solution.The Weight-average molecular of Resin A b of gained
Amount Mw is 13,400, molecular weight distribution（Mw/Mn）For 2.50.
The weight average molecular weight of the resin obtaining in above-mentioned（Mw）And number-average molecular weight（Mn）Mensure use GPC method, with
Carry out under conditions of lower.
Device；K2479（（Strain）Shimadzu Seisakusho Ltd.'s system）
Pillar；SHIMADZU Shim-pack GPC-80M
Column temperature；40℃
Solvent；THF（Oxolane）
Flow velocity；1.0mL/min
Detector；RI
Correction standard substance；TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-
500（Eastern ソ（Strain）System）
Ratio by the weight average molecular weight of polystyrene conversion obtained above and number-average molecular weight（Mw/Mn）As molecule
Amount distribution.
（Embodiment 1～8 and comparative example 1）
By the composition mixing of table 1, obtain hardening resin composition.
【Table 1】
And, in table 1, unless otherwise specified, unit is " part ".Polymer（A）Containing number represent solid become
Divide the mass parts of conversion.
Polymer（A）；Aa；Resin A a obtaining in synthesis example
Polymer（A）；Ab；Resin A b obtaining in synthesis example
（Methyl）Acyclic compound（B）；Ba；Dipentaerythritol acrylate（KAYARAD（Registered trade mark） DPHA；
Japanese chemical medicine（Strain）System）
Polymerization initiator（C）；Ca；N- benzoyloxy -1-（4- Phenylsulfanyl phenyl）Octane -1- ketone -
2- imines（イルガキュア（Registered trade mark）OXE 01；BASF society system；Oxime compound）
Polymerization initiator（C）；Cb；2,2 '-bis-（2- chlorphenyl）- 4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline
（B-CIM；Hodogaya chemical（Strain）System）
Polymerization causes auxiliary agent（C1）；C1a；2-（2- naphthoyl methylene）- 3- methylbenzothiazole quinoline
Imidazolium compoundss（D）；Da；1- benzyl -2- phenylimidazole（キュアゾール1B2PZ；Four countries' chemical conversion industry
（Strain）System）
【Change 10】
Imidazolium compoundss（D）；Db；1-（2- cyano ethyl）- 2- undecyl imidazole（キ ュ ア ゾ Le C11Z-
CN；Four countries' chemical conversion industry（Strain）System）
【Change 11】
Imidazolium compoundss（D）；Dc；1-（2- cyano ethyl）- 2-ethyl-4-methylimidazole（キュアゾール
2E4MZ-CN；Four countries' chemical conversion industry（Strain）System）
【Change 12】
Mercaptan compound（T）；Ta；Pentaerythritoltetrakispropionate（PEMP；SC organic chemistry（Strain）System）
Antioxidant（F）；Fa；1,3,5- tri-（4- hydroxyl -3,5- di-t-butyl benzyl）- 1,3,5-triazines -2,
4,6（1H, 3H, 5H）- triketone（IRGANOX（Registered trade mark）3114；BASFジャパン（Strain）System）
Solvent（E）；Ea；Propylene glycol monomethyl ether
Solvent（E）；Eb；3- methoxyl group-n-butyl alcohol
Solvent（E）；Ec；Diethylene glycol ethyl-methyl ether
Solvent（E）；Ed；3- ethoxy ethyl propionate
Solvent（E）；Ee；3- methoxybutyl acetass
By solvent（E）Mixing, so that the solid component amount of hardening resin composition is " the solid component amount of table 1
（%）", solvent（E）In solvent composition（Ea）~（Ee）Value represent solvent（E）In mass ratio.
＜ viscosimetric analysis ＞
For the hardening resin composition of gained, respectively using viscometer（Type；TV-30；Eastern machine industry（Strain）System）
To measure viscosity.Result is shown in table 2.
The transmission coefficient ＞ of ＜ hardening resin composition
For the hardening resin composition of gained, respectively using UV, visible light near infrared spectrometer（V-650；Day
This light splitting（Strain）System）（Quartz cell, light path；1cm）Measure the average transmission coefficient of 400～700nm（%）.Result is shown in table 2.
The making ＞ of ＜ film
The foursquare glass substrate that the length of side is 2 inches（イーグルXG；Conning society system）Use neutrality successively
After lotion, water and 2- propanol rinse, it is dried.Spin coating hardening resin composition on this glass substrate is so as in after bake
Thickness afterwards is 3.0 μm, then in heating plate, 90 DEG C of preliminary dryings 2 minutes, is then used by exposure machine（TME-150RSK；トプコ
ン（Strain）System, light source；Extra-high-pressure mercury vapour lamp）Under air atmosphere, with 100mJ/cm2Light exposure（365nm benchmark）By preliminary drying
Film afterwards is exposed.And, in this exposure, make the radiating light from extra-high-pressure mercury vapour lamp pass through light filter（UV-33；
Rising sun テ Network ノ グ ラ ス（Strain）System）It is irradiated.After exposure, heat 20 minutes at 230 DEG C, obtain film.
The transmission coefficient ＞ of ＜ film
For the film of gained, using microspectrophotometer device（OSP-SP200；OLYMPUS society system）To measure
The average transmission coefficient of 400～700nm（%）.Result is shown in table 2.
＜ thermostability ＞
The film of gained is heated 60 minutes in 240 DEG C of baking oven, measures the thickness before and after heating and transmission coefficient, press
According to following formula, try to achieve Thickness Variation（%）And variations in transmissivity（%）.And, thickness uses film thickness measuring device（DEKTAK3；
Japanese vacuum technique（Strain）System）It is measured.Both of which is closer to 100%, shows that the change before and after heating is less, thermostability
More excellent.In addition, if the thermostability of film is high, then the thermostability of the pattern being formed by identical hardening resin composition
High.Result is shown in table 2.
Variations in transmissivity（%）；（Transmission coefficient after heating（%）Transmission coefficient before/heating（%））×100
Thickness Variation（%）；（Thickness after heating（μm）Thickness before/heating（μm））×100
＜ pattern forms ＞
The foursquare glass substrate that the length of side is 2 inches（イーグル2000；Conning society system）In using successively
After property lotion, water and 2- propanol rinse, it is dried.On this glass substrate, with spin coater coating curable resin combination
Thing, so that the thickness of the pattern after after bake is 3 μm.Then, using pressure Reduction Dryer（VCDマイクロテック（Strain）System）Will
Degree of decompression is decompressed to 0.5torr, is dried, and forms film.By this film in heating plate, 90 DEG C carry out the preliminary drying of 2 minutes.
The interval of substrate and quartz glass photomask is set to 10 μm, using exposure machine（TME-150RSK；トプコン（Strain）System,
Light source；Extra-high-pressure mercury vapour lamp）, under air atmosphere, using 100mJ/cm2Light exposure（365nm benchmark）By pre-baked painting
Film exposes.And in this exposure, make the radiating light from extra-high-pressure mercury vapour lamp pass through light filter（UV-33；Rising sun テ Network ノ グ
ラス（Strain）System）To be irradiated.As above-mentioned photomask, employ to define at grade there are a diameter of 5 μm, 6 μ
The circle of m, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm and 20 μm is thoroughly
The photomask of the pattern being spaced apart 100 μm of light portion and this circular transmittance section.
After exposure, in the water system developer solution containing nonionic surfactants 0.12% and potassium hydroxide 0.04%,
Impregnate 60 seconds at 25 DEG C, developed, after washing, carry out the after bake of 20 minutes using baking oven at 230 DEG C, form pattern.
＜ resolution evaluates ＞
Observation utilizes scanning electron microscope（S-4000；（Strain）Society of Hitachi system）The pattern obtaining, by pattern
Detached minimum feature is as resolution.Result is shown in table 2.
【Table 2】
By the above results it has been confirmed that the film being obtained using the hardening resin composition of the present invention, try in thermostability
Variations in transmissivity in testing is little, and the coloring being led to by heat treated is few.
Industry utilizability
According to the hardening resin composition of the present invention, film and the pattern of excellent heat resistance can be formed.
Claims (4)
1. hardening resin composition, it contains following（A）、（B）、（C）With（D）,
（A）Have containing coming from least one construction unit in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and coming from
The addition polymers of the construction unit of the unsaturated compound of Oxyranyle,
（B）Have the compound of at least one group in acryloyl group and methylacryloyl,
（C）Polymerization initiator,
（D）Formula（1）Shown compound,
【Change 13】
Formula（1）In, R1Expression benzyl or the cyanoalkyl that carbon number is 2～5,
R2～R4Represent that alkyl, phenyl, nitro or carbon that hydrogen atom, halogen atom, carbon number are 1～20 are former independently of each other
Subnumber is 1～20 acyl group, and the hydrogen atom containing in this alkyl and this phenyl can be optionally substituted by a hydroxyl group.
2. hardening resin composition as claimed in claim 1, wherein,（D）Content with respect to（A）100 mass parts are 1 matter
Amount part～25 mass parts.
3. film, it is formed using the hardening resin composition described in claim 1 or 2.
4. display device, it contains film as claimed in claim 3.
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| CN104865794A (en) * | 2014-02-20 | 2015-08-26 | 上海飞凯光电材料股份有限公司 | Photoresist |
| JP6695369B2 (en) * | 2017-02-16 | 2020-05-20 | 住友化学株式会社 | Curable resin composition, cured film and display device |
| CN116814179B (en) * | 2023-01-31 | 2024-02-27 | 江苏穿越光电科技有限公司 | UV light-cured optical adhesive film |
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| JP2715792B2 (en) * | 1992-02-13 | 1998-02-18 | 信越化学工業株式会社 | Light transmitting epoxy resin composition and optical semiconductor device |
| JP3586933B2 (en) * | 1995-08-09 | 2004-11-10 | Ｊｓｒ株式会社 | Curable composition, protective film, and method for producing protective film |
| JP4606684B2 (en) * | 2000-03-29 | 2011-01-05 | 学校法人神奈川大学 | Photocurable / thermosetting resin composition, photosensitive dry film thereof and pattern forming method using the same |
| WO2002077058A1 (en) * | 2001-03-23 | 2002-10-03 | Taiyo Ink Manufacturing Co., Ltd. | Resin curable with actinic energy ray, photocurable/thermosetting resin composition containing the same, and cured article obtained therefrom |
| US20050203239A1 (en) * | 2002-06-20 | 2005-09-15 | Sumio Shibahara | Transparent composite composition |
| JP3937996B2 (en) * | 2002-10-08 | 2007-06-27 | Ｊｓｒ株式会社 | Radiation sensitive resin composition |
| KR100845657B1 (en) * | 2004-07-07 | 2008-07-10 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable/thermosetting resin composition, dry film using same, and cured product thereof |
| JP2007182539A (en) * | 2005-12-06 | 2007-07-19 | Jsr Corp | Resin composition, method for forming preventive film of color filter and preventive film of the color filter |
| JP5224030B2 (en) * | 2007-03-22 | 2013-07-03 | Ｊｓｒ株式会社 | Thermosetting resin composition, protective film and method for forming protective film |
| US20100068650A1 (en) * | 2007-03-28 | 2010-03-18 | Yukio Nishimura | Positive-working radiation-sensitive composition and method for resist pattern formation using the composition |
| US8084545B2 (en) * | 2007-05-11 | 2011-12-27 | Daicel Chemical Industries, Ltd. | Photo- and/or thermo-curable copolymer, curable resin compositions, and cured articles |
| TWI422601B (en) * | 2007-11-29 | 2014-01-11 | Sumitomo Chemical Co | Thermosetting resin composition |
| TWI521300B (en) * | 2008-11-18 | 2016-02-11 | Sumitomo Chemical Co | Photosensitive resin composition and display device |
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